Tire compositions and components containing free-flowing filler compositions

ABSTRACT

Free-flowing filler compositions containing silated cyclic core polysulfide coupling agents, and rubber and tire compositions containing the filler compositions.

The present application is directed to an invention which was developedpursuant to a joint research agreement within the meaning of 35 U.S.C.§103(c). The joint research agreement dated May 7, 2001 as amended,between Continental AG, and General Electric Company, on behalf of GEAdvanced Materials, Silicones Division, now Momentive PerformanceMaterials Inc.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is related to the following application, filedon even date herewith, with the disclosures of each the applicationsbeing incorporated by reference herein in their entireties:

Application Ser. No. 11/617,683, filed Dec. 28, 2006, entitled TireCompositions And Components Containing Silated Cyclic Core Polysulfides.

Application Ser. No. 11/617,663, filed Dec. 28, 2006, entitled TireCompositions And Components Containing Silated Core Polysulfides.

Application Ser. No. 11/617,649, filed Dec. 28, 2006, entitled TireCompositions And Components Containing Free-Flowing Filler Compositions.

Application Ser. No. 11/617,659, filed Dec. 28, 2006, entitled TireCompositions and Components Containing Blocked Mercaptosilane CouplingAgent.

Application Ser. No. 11/648,460, filed Dec. 28, 2006, entitledFree-Flowing Filler Composition And Rubber Composition Containing Same.

Application Ser. No. 11/647,903, filed Dec. 28, 2006, entitledFree-Flowing Filler Composition And Rubber Composition Containing Same.

Application Ser. No. 11/647,780, filed Dec. 28, 2006, entitled BlockedMercaptosilane Coupling Agents, Process For Making And Uses In Rubber.

Application Ser. No. 11/648,287, filed Dec. 28, 2006, entitled SilatedCore Polysulfides, Their Preparation And Use In Filled ElastomerCompositions.

Application Ser. No. 11/647,901, filed Dec. 28, 2006, entitled SilatedCyclic Core Polysulfides, Their Preparation And Use In Filled ElastomerCompositions.

FIELD OF THE INVENTION

The present invention generally relates to filler compositions, moreparticularly, to free-flowing filler compositions containing, or derivedfrom, silated cyclic core polysulfides, and to tire compositions andtire components containing the filler composition.

BACKGROUND OF THE INVENTION

Fuel economies and the need to protect the environment are economic andsocietal priorities. As a result, it has become desirable to produceelastomers with good mechanical properties so that they can be used inthe form of rubber compositions usable for the construction of tireswith improved properties, having in particular reduced rollingresistance.

To this end, numerous solutions have been proposed, such as, forexample, the use of coupling, starring or functionalizing agents withreinforcing filler to modify elastomers with the goal of obtaining agood interaction between the modified elastomer and the reinforcingfiller. In order to obtain the optimum reinforcement properties impartedby a filler, the filler is preferably present in the elastomeric matrixin a final form which is both as finely divided as possible anddistributed as homogeneously as possible.

Without being bound by theory, filler particles tend to attract to oneanother and agglomerate within the elastomeric matrix. As such, there isa reduction in the number of filler-elastomer bonds created during themixing process. As a result of these interactions the consistency of therubber composition increases and makes processing more difficult.

Rubber compositions reinforced with fillers, such as, aluminas oraluminum (oxide-)hydroxides, of high dispersibility, andsulfur-vulcanizable diene rubber composition, reinforced with a specialprecipitated silica of the highly dispersible type, are know in the art.Use of these fillers makes it possible to obtain tires or treads withimproved rolling resistance, without adversely affecting the otherproperties, in particular those of grip, endurance and wear resistance.Although the use of these specific, highly reinforcing, siliceous oraluminous fillers has reduced the difficulties of processing the rubbercompositions that contain them, such rubber compositions arenevertheless more difficult to process than rubber compositions filledconventionally with carbon black.

In particular, it is necessary to use a coupling agent, also known as abonding agent, the function of which is to provide the connectionbetween the surface of the filler particles and the elastomer, whilefacilitating the dispersion of this filler within the elastomericmatrix.

Sulfur-containing coupling agents used for mineral-filled elastomersinvolve silanes in which two alkoxysilylalkyl groups are bound, each toone end of a chain of sulfur atoms. The two alkoxysilyl groups arebonded to the chain of sulfur atoms by two similar, and in most cases,identical, hydrocarbon fragments. The general silane structures justdescribed, hereinafter referred to as “simple bis polysulfide silanes,”usually contain a chain of three methylene groups as the two mediatinghydrocarbon units. In some cases, the methylene chain is shorter,containing only one or two methylenes per chain. The use of thesecompounds is primarily as coupling agents for mineral-filled elastomersThese coupling agents function by chemically bonding silica or othermineral fillers to polymer when used in rubber applications. Withoutbeing bound by theory, it is believed that coupling is accomplished bychemical bond formation between the silane sulfur and the polymer and byhydrolysis of the alkoxysilyl groups and subsequent condensation withsilica hydroxyl groups. It is further believed that the reaction of thesilane sulfur with the polymer occurs when the S—S bonds are broken andthe resulting fragment adds to the polymer. It is further believed thata single linkage to the polymer occurs for each silyl group bonded tothe silica. This linkage contains a single, relatively weak C—S and/orS—S bond(s) that forms the weak link between the polymer and the silica.Under high stress, this single C—S and/or S—S linkages may break andtherefore contribute to wear of the filled elastomer.

The use of polysulfide silanes coupling agents in the preparation ofrubber is well known. These silanes contain two silicon atoms, each ofwhich is bound to a disubstituted hydrocarbon group, and three othergroups of which at least one is removable from silicon by hydrolysis.Two such hydrocarbon groups, each with their bound silyl group, arefurther bound to each end of a chain of at least two sulfur atoms. Thesestructures thus contain two silicon atoms and a single, continuous chainof sulfur atoms of variable length.

Hydrocarbon core polysulfide silanes that feature a central molecularcore isolated from the silicon in the molecule by sulfur-sulfur bondsare known in the art. Polysulfide silanes containing a core that is anaminoalkyl group separated from the silicon atom by a single sulfur anda polysulfide group and where the polysulfide group is bonded to thecore at a secondary carbon atom are also known in the art. As well ascore fragments in which only two polysulfide groups are attached to thecore.

However, polysulfide groups that are attached directly to an aromaticcore have reduced reactivity with the polymer (rubber). The aromaticcore is sterically bulky which may inhibit the reaction. Compositions inwhich the polysulfides are attached directly to cyclic aliphaticfragments derived by vinyl cyclohexene contain more than one silatedcore and form large rings. The cyclohexyl core is sterically morehindered than the aromatic core and is less reactive. Although thesecompositions may be able to form more than one sulfur linkage to thepolymer rubber for each attachment of the coupling agent to the silicathrough the silyl group, their effectiveness is low probably due to thelow reactivity.

Without being bound by theory, the low reactivity is due to theattachment of the polysulfide to the secondary carbon of cyclic corestructure. The positioning of the polysulfide group is not optimal forreaction with the accelerators and reaction with the polymer.

The present invention overcomes the deficiencies of the aforementionedcompositions involving silane coupling agents in several ways. Thesilanes of the present invention described herein are not limited to twosilyl groups nor to one chain of sulfur atoms. In fact, the moleculararchitecture of the present invention includes multiple polysulfidechains which are oriented in a noncollinear configuration (i.e.,branched, in the sense that the branch points occur within the carbonbackbone interconnecting the polysulfide chains), and provide a novelconfiguration.

The fillers of the present invention have advantages over that in theprior art by providing multiple points of sulfur attachment to polymerper point of silicon attachment to filler. The silanes of the fillersdescribed herein may be asymmetric with regard to the groups on the twoends of the sulfur chains. The silyl groups, rather than occurring atthe ends of the molecule, tend to occur more centrally and arechemically bonded to the core through carbon-carbon, carbon-sulfur andcarbon-silicon bonds. The carbon-sulfur bonds of the thio ester linkages(sulfide) are more stable than the sulfur-sulfur bonds of the disulfideor polysulfide functional groups. These thio ether groups are thereforeless likely to react with the accelerators and curing agents or todecompose when subjected to high shear or temperatures normallyassociated with the mixing and curing of rubber compounds. The thioether linkage also provide a convenient synthetic route for making thesilanes of the present invention. The cyclic core also contains multiplepolysulfide groups that are attached to ring by a divalent, straightchain alkylene group. The attachment of the polysulfide group to theprimary carbon of the alkylene group decreases significantly the sterichindrance of the core, and increases the reactivity of the polysulfideswith the polymer. In addition, the cyclic core orients these alkylenechains containing the polysulfide groups away from each other to furtherreduce the steric hindrance near the polysulfide groups. Thisdistinction is what allows silane silicon to become and remain bonded(through the intermediacy of a sequence of covalent chemical bonds) topolymer at multiple points using the silanes of the present invention.

Also, without being bound by theory, silated core silanes of the presentinvention include a Y-core structure. This Y-core structure is believedto enable bonding the polymer at two different points or crosslinking ontwo different polymer chains, and also enables attachment, such as bybonding, to a filler.

SUMMARY OF THE INVENTION

In a first embodiment of the present invention, a preformed,free-flowing filler composition, such as for use in tire compositions,is provided which comprises:

a) a filler;

b) a first silane which is a silated cyclic-core polysulfide having thegeneral formula[Y¹R¹S_(x)—]_(m)[G¹(—SR²SiX¹X²X³)_(a)]_(n)[G²]_(o)[R³Y²]_(p)  (Formula1)

wherein:

each occurrence of G¹ is independently selected from a polyvalent cyclichydrocarbon or polyvalent cyclic heterocarbon species having from 1 toabout 30 carbon atoms containing a polysulfide group represented by thegeneral formula:[(CH₂)_(b)—]_(c)R⁴[—(CH₂)_(d)S_(x)—]_(e);  (Formula 2)

each occurrence of G² is independently selected from a polyvalent cyclichydrocarbon or polyvalent cyclic heterocarbon species of 1 to about 30carbon atoms containing a polysulfide group represented by the generalformula:[(CH₂)_(b)—]_(c)R⁵[—(CH₂)_(d)S_(x)—]_(e);  (Formula 3)

each occurrence of R¹ and R³ is independently selected from a divalenthydrocarbon fragment having from 1 to about 20 carbon atoms;

each occurrence of Y¹ and Y² is independently selected from silyl(—SiX¹X²X³), hydrogen, alkoxy (—OR⁶), carboxylic acid, ester(—C(═O)OR⁶), wherein R⁶ is a monovalent hydrocarbon group having from 1to 20 carbon atoms;

each occurrence of R² is independently selected from a divalenthydrocarbon fragment having from 1 to about 20 carbon atoms that includebranched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkylgroups;

each occurrence of R⁴ is independently selected from a polyvalent cyclichydrocarbon fragment of 1 to about 28 carbon atom that was obtained bysubstitution of hydrogen atoms equal to the sum of a+c+e, and includecyclic and polycyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groupsin which a+c+e−1 hydrogens have been replaced, or a polyvalent cyclicheterocarbon fragment from 1 to 27 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of a+c+e;

each occurrence of R⁵ is independently selected from a polyvalent cyclichydrocarbon fragment of 1 to about 28 carbon atom that was obtained bysubstitution of hydrogen atoms equal to the sum of c+e and includecyclic and polycyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groupsin which c+e−1 hydrogens have been replaced, or a polyvalent cyclicheterocarbon fragment from 1 to 27 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of c+e;

each occurrence of X¹ is independently selected from —Cl, —Br, —OH,—OR⁶, and R⁶C(═O)O—, wherein R⁶ is a monovalent hydrocarbon group havingfrom 1 to 20 carbon atoms;

each occurrence of X² and X³ is independently selected from hydrogen,R⁶, wherein R⁶ is a monovalent hydrocarbon group having from 1 to 20carbon atoms, X¹, wherein X¹ is independently selected from the groupconsisting of —Cl, —Br, —OH, —OR⁶, and R⁶C(═O)O—, wherein R⁶ is amonovalent hydrocarbon group having from 1 to 20 carbon atoms , and —OSicontaining groups that result from the condensation of silanols; and

each occurrence of the subscripts, a, b, c, d, e, m, n, o, p, and x, isindependently given by a, c and e are 1 to about 3; b is 1 to about 5; dis 1 to about 5; m and p are 1 to about 100; n is 1 to about 15; o is 0to about 10; and x is 1 to about 10; and, optionally,

c) a second silane having the general formula[X¹X²X³SiR¹S_(x)R³SiX¹X²X³]  (Formula 4)wherein;

each occurrence of R¹ and R³ are chosen independently from a divalenthydrocarbon fragment having from 1 to about 20 carbon atoms that includebranched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkylgroups wherein one hydrogen atom was substituted with a silyl group(—SiX¹X²X³), wherein X¹ is independently selected from —Cl, —Br, —OH,—OR⁶, and R⁶C(═O)O—, wherein R⁶ is any monovalent hydrocarbon grouphaving from 1 to 20 carbon atoms, and includes branched or straightchain alkyl, alkenyl, aryl or aralkyl group and X² and X³ isindependently selected from the group consisting of hydrogen, R⁶, X¹,and —OSi containing groups that result from the condensation ofsilanols.

In a second embodiment of the present invention, rubber compositions areprovided, such as for use in a tire composition, comprising at least onerubber, at least one free-flowing filler composition of the presentinvention, a curative and, optionally, at least one other additiveselected from the group consisting of sulfur compounds, activators,retarders, accelerators, processing additives, oils, plasticizers,tackifying resins, silicas, fillers, pigments, fatty acids, zinc oxide,waxes, antioxidants and antiozonants, peptizing agents, reinforcingmaterials, and mixtures thereof.

The present invention is also directed to tire compositions for forminga tire component, the compositions formed by combining at least apreformed free-flowing filler composition and at least one vulcanizablerubber selected from natural rubbers, synthetic polyisoprene rubbers,polyisobutylene rubbers, polybutadiene rubbers, and randomstyrene-butadiene rubbers (SBR);

the preformed free-flowing filler composition formed by combining atleast an active filler and a first silane;

the active filler including at least one of active filler selected fromcarbon blacks, silicas, silicon based fillers, and metal oxides presentin a combined amount of at least 35parts by weight per 100 parts byweight of total vulcanizable rubber, of which at least 10 parts byweight is carbon black, silica, or a combination thereof; and

the first silane comprising at least one silated cyclic core polysulfidehaving the general formula[Y¹R¹S_(x)—]_(m)[G¹(—SR²SiX¹X²X³)_(a)]_(n)[G²]_(o)[R³Y²]_(p)

wherein:

each occurrence of G¹ is independently selected from a polyvalent cyclichydrocarbon or polyvalent cyclic heterocarbon species having from 1 toabout 30 carbon atoms containing a polysulfide group represented by thegeneral formula:[(CH₂)_(b)—]_(c)R⁴[—(CH₂)_(d)S_(x)—]_(e);

each occurrence of G² is independently selected from a polyvalent cyclichydrocarbon or polyvalent cyclic heterocarbon species of 1 to about 30carbon atoms containing a polysulfide group represented by the generalformula:[(CH₂)_(b)—]_(c)R⁵[—(CH₂)_(d)S_(x)—]_(e);

each occurrence of R¹ and R³ is independently selected from a divalenthydrocarbon fragment having from 1 to about 20 carbon atoms;

each occurrence of Y¹ and Y² is independently selected from consistingof silyl (—SiX¹X²X³), hydrogen, alkoxy (—OR⁶), carboxylic acid, ester(—C(═O)OR⁶) wherein R⁶ is a monovalent hydrocarbon group having from 1to 20 carbon atoms;

each occurrence of R² is independently selected from a divalenthydrocarbon fragment having from 1 to about 20 carbon atoms that includebranched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkylgroups;

each occurrence of R⁴ is independently selected from a polyvalent cyclichydrocarbon fragment of 1 to about 28 carbon atom that was obtained bysubstitution of hydrogen atoms equal to the sum of a+c+e, and includecyclic and polycyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groupsin which a+c+e−1 hydrogens have been replaced, or a polyvalent cyclicheterocarbon fragment from 1 to 27 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of a+c+e;

each occurrence of R⁵ is independently selected from a polyvalent cyclichydrocarbon fragment of 1 to about 28 carbon atom that was obtained bysubstitution of hydrogen atoms equal to the sum of c+e and includecyclic and polycyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groupsin which c+e−1 hydrogens have been replaced, or a polyvalent cyclicheterocarbon fragment from 1 to 27 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of c+e;

each occurrence of X¹ is independently selected from —Cl, —Br, —OH,—OR⁶, and R⁶C(═O)O—, wherein R⁶ is a monovalent hydrocarbon group havingfrom 1 to 20 carbon atoms;

each occurrence of X² and X³ is independently selected from hydrogen,R⁶, wherein R⁶ is a monovalent hydrocarbon group having from 1 to 20carbon atoms, X¹, wherein X¹ is independently selected from —Cl, —Br,—OH, —OR⁶, and R⁶C(═O)O—, wherein R⁶ is a monovalent hydrocarbon grouphaving from 1 to 20 carbon atoms , and —OSi containing groups thatresult from the condensation of silanols; and

each occurrence of the subscripts, a, b, c, d, e, m, n, o, p, and x, isindependently given by a, c and e are 1 to about 3; b is 1 to about 5; dis 1 to about 5; ; m and p are 1 to about 100; n is 1 to about 15; o is0 to about 10; and x is 1 to about 10; and

wherein the tire composition is formulated to be vulcanizable to form atire component compound having a Shore A Hardness of not less than 40and not greater than 95 and a glass-transition temperature Tg (E″_(max))not less than −80° C. and not greater than 0° C.

The present invention is also directed to tires at least one componentof which comprises cured tire compositions obtained from rubbercompositions according to the present invention.

The present invention is also directed to tire components, cured anduncured, including, but not limited to, tire treads, including any tirecomponent produced from any composition including at least a silatedcore polysulfide.

The examples presented herein demonstrate that the fillers of thepresent invention impart a desirable balance of physical properties(performance to mineral-filled elastomer compositions) and better wearcharacteristics to articles manufactured from these elastomers,including tires and tire components. Improvements in rolling resistanceare also apparent for elastomers used in tire applications.

The compositions of the present invention exhibit excellent dispersionof filler is and can achieve excellent workability, and improvedproductivity in vulcanization.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is further described in the detailed descriptionthat follows by way of non-limiting examples of exemplary embodiments ofthe present invention, wherein:

FIG. 1 shows HPLC analysis of the product of Example 1.

DEFINITIONS

In describing and claiming the present invention, the followingterminology will be used.

The term “coupling agent” as used herein includes an agent capable ofestablishing a sufficient chemical and/or physical connection betweenthe filler and the elastomer. Such coupling agents have functionalgroups capable of bonding physically and/or chemically with the filler,for example, between a silicon atom of the coupling agent and thehydroxyl (OH) surface groups of the filler (e.g., surface silanols inthe case of silica); and, for example, sulfur atoms which are capable ofbonding physically and/or chemically with the elastomer.

The term “filler” as used herein includes a substance that is added tothe elastomer to either extend the elastomer or to reinforce theelastomeric network. Reinforcing fillers are materials whose moduli arehigher than the organic polymer of the elastomeric composition and arecapable of absorbing stress from the organic polymer when the elastomeris strained, Fillers include fibers, particulates, and sheet-likestructures and can be composed of inorganic minerals, organosiliconcompounds, such as, by way of nonlimiting example, silanes, silicones,and polysiloxanes, and intermediates comprising monomers and reactiveadditives having a silicon atom, and any other molecule, oligomer,polymer or interpolymer which contains a silicon atom and a carbon atom,silicates, silica, clays, ceramics, carbon, organic polymers,diatomaceous earth. The filler of the present invention can beessentially inert to the silane with which it is admixed, or it can bereactive therewith.

The term “particulate filler” or “particulate composition” as usedherein includes a particle or grouping of particles to form aggregatesor agglomerates, including reinforcement filler or particles, includingwithout limitation, those containing or made from organic molecules,oligomers, and/or polymers, e.g., poly(arylene ether) resins, orfunctionalized reinforcement filler or particle. The term functionalizedis intended to include any particles treated with an organic molecule,polymer, oligomer, or otherwise (collectively, treating agent(s)),thereby chemically bonding the treating agent(s) to the particle. Theparticulate filler of the present invention can be essentially inert tothe silane with which it is admixed, or it can be reactive therewith.

The term “carrier” as used herein includes a porous or high surface areafiller that has a high adsorption or absorption capability and iscapable of carrying up to 75 percent liquid silane while maintaining itsfree-flowing and dry properties. The carrier filler of the presentinvention is essentially inert to the silane and is capable of releasingor deabsorbing the liquid silane when added to the elastomericcomposition.

The term “preformed” as used herein shall be understood to include afiller composition that is prepared prior to its addition to a rubber ormixture of rubbers.

The term “rubber” includes natural or synthetic elastomers, includingpolyisoprene rubbers, polyisobutylene rubbers, polybutadiene rubbers andstyrenebutadiene rubbers.

The term “tire compositions” includes those compositions useful for themanufacture of tires or tire components, and includes rubbercompositions that include at least one rubber, a silane or afree-flowing filler composition containing, or derived from, silatedcore polysulfide, and at least one active filler such as, by way ofnonlimiting example, carbon blacks, silicas, silicon based fillers, andmetal oxides present either alone or in combination. For example, anactive filler may be selected from the group described above (e.g.,carbon blacks, silicas, silicon based fillers, and metal oxides) and maybe, but does not have to be, present in a combined amount of at least 35parts by weight per 100 parts by weight of total vulcanizable rubber, ofwhich at least 10 parts can be carbon black, silica, or some combinationthereof, and wherein said compositions can be formulated so that theyare vulcanizable to form a tire component compound. The tire componentcompounds may have a Shore A Hardness of not less than 40 and notgreater than 95 and a glass-transition temperature Tg (E″_(max)) notless than −80° C. and not greater than 0° C. The Shore A Hardness ismeasured in accordance with DIN 53505. The glass-transition temperatureTg (E″_(max)) is measured in accordance with DIN 53513 with a specifiedtemperature sweep of −80° C. to +80° C. and a specified compression of10±0.2% at 10 Hz.

DETAILED DESCRIPTIONS OF THE PRESENT INVENTION

The free-flowing filler composition of the present invention is apreformed, free-flowing filler composition for use in a tire compositionwhich comprises:

a) a filler;

b) a first silane which is a silated cyclic core polysulfide having thegeneral formula[Y¹R¹S_(x)—]_(m)[G¹(—SR²SiX¹X²X³)_(a)]_(n)[G²]_(o)[R³Y²]_(p)  (1)is provided, wherein each occurrence of G¹ is independently selectedfrom polyvalent cyclic hydrocarbon or polyvalent cyclic heterocarbonspecies having from 1 to about 30 carbon atoms and containing apolysulfide group represented by Formula (2)[(CH₂)_(b)—]_(c)R⁴[—(CH₂)_(d)S_(x)—]_(e);  (2)

each occurrence of G² is independently selected from a polyvalent cyclichydrocarbon or polyvalent cyclic heterocarbon species of 1 to about 30carbon atoms and containing a polysulfide group represented by Formula(3)[(CH₂)_(b)—]_(c)R⁵[—(CH₂)_(d)S_(x)—]_(e);  (3)

each occurrence of R¹ and R³ are independently selected from a divalenthydrocarbon fragment having from 1 to about 20 carbon atoms that includebranched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkylgroups in which one hydrogen atom was substituted with a Y¹ or Y² group;

each occurrence of Y¹ and Y² is independently selected from, but notlimited to silyl (—SiX¹X²X³), alkoxy (—OR⁶), hydrogen, carboxylic acid(—C(═O)OH), ester (—C(═O)OR⁶, in which R⁶ is any monovalent hydrocarbongroup having from 1 to 20 carbon atoms, and includes branched orstraight chain alkyl, alkenyl, aryl or aralkyl groups and the like;

each occurrence of R² is independently selected from a divalenthydrocarbon fragment having from 1 to about 20 carbon atoms that includebranched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkylgroups;

each occurrence of R⁴ is independently selected from a polyvalent cyclichydrocarbon fragment of 1 to about 28 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of a+c+e, and includecyclic and polycyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groupsin which a+c+e−1 hydrogens have been replaced, or a polyvalent cyclicheterocarbon fragment from 1 to 27 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of a+c+e;

each occurrence of R⁵ is independently selected from a polyvalent cyclichydrocarbon fragment of 1 to about 28 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of c+e and includecyclic and polycyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groupsin which c+e−1 hydrogens have been replaced, or a polyvalent cyclicheterocarbon fragment from 1 to 27 carbon atoms that was obtained bysubstitution of hydrogen atoms equal to the sum of c+e;

each occurrence of X¹ is independently selected from hydrolysable groups—Cl, —Br, —OH, —OR⁶, and R⁶C(═O)O—, wherein R⁶ is any monovalenthydrocarbon group having from 1 to 20 carbon atoms, and includesbranched or straight chain alkyl, alkenyl, aryl or aralkyl groups;

each occurrence of X² and X³ is independently selected from hydrogen,the members listed above for R⁶, the members listed above for X¹ and—OSi containing groups that result from the condensation of silanols;

each occurrence of the subscripts, a, b, c, d, e, m, n, o, p, and x, isindependently given by a is 1 to about 3; b is 1 to about 5; c is 1 toabout 3; d is 1 to about 5; e is 1 to about 3; ; m is 1 to about 100, nis 1 to about 15; o is 0 to about 10; p is 1 to about 100, and x is 1 toabout 10; and, optionally,

c) a second silane having the general formula[X ¹X²X³SiR¹S_(x)R³SiX¹X²X³]  (4)wherein;

each occurrence of each occurrence of R¹ and R³ are chosen independentlyfrom a divalent hydrocarbon fragment having from 1 to about 20 carbonatoms that include branched and straight chain alkyl, alkenyl, alkynyl,aryl or aralkyl groups wherein one hydrogen atom was substituted with asilyl group, (—SiX¹X²X³), wherein X¹ is independently selected from —Cl,—Br, —OH, —OR⁶, and R⁶C(═O)O—, wherein R⁶ is any monovalent hydrocarbongroup having from 1 to 20 carbon atoms, and includes branched orstraight chain alkyl, alkenyl, aryl or aralkyl group and X² and X³ isindependently selected from hydrogen, R⁶, X¹, and —OSi containing groupsthat result from the condensation of silanols.

The term, “heterocarbon”, as used herein, refers to any hydrocarbonstructure in which the carbon-carbon bonding backbone is interrupted bybonding to hetero atoms, such as atoms of nitrogen, sulfur, phosphorusand/or oxygen, or in which the carbon-carbon bonding backbone isinterrupted by bonding to groups of atoms containing sulfur, nitrogenand/or oxygen, such as cyanurate (C₃N₃). Heterocarbon fragments alsorefer to any hydrocarbon in which a hydrogen or two or more hydrogensbonded to carbon are replaced with a sulfur, oxygen or nitrogen atom,such as a primary amine (—NH₂), and oxo (═O), and the like.

Thus, R⁴ and R⁵ include, but is not limited to cyclic, and/or polycyclicpolyvalent aliphatic hydrocarbons that may be substituted with alkyl,alkenyl, alkynyl, aryl and/or aralkyl groups; cyclic and/or polycyclicpolyvalent heterocarbon optionally containing ether functionality viaoxygen atoms each of which is bound to two separate carbon atoms,polysulfide functionality, in which the polysulfide group (—S_(x)—) isbonded to two separate carbon atoms on G¹ or G² to form a ring, tertiaryamine functionality via nitrogen atoms each of which is bound to threeseparate carbon atoms, cyano (CN) groups, and/or cyanurate (C₃N₃)groups; aromatic hydrocarbons; and arenes derived by substitution of theaforementioned aromatics with branched or straight chain alkyl, alkenyl,alkynyl, aryl and/or aralkyl groups.

As used herein, “alkyl” includes straight, branched and cyclic alkylgroups; “alkenyl” includes any straight, branched, or cyclic alkenylgroup containing one or more carbon-carbon double bonds, where the pointof substitution can be either at a carbon-carbon double bond orelsewhere in the group; and “alkynyl” includes any straight, branched,or cyclic alkynyl group containing one or more carbon-carbon triplebonds and optionally also one or more carbon-carbon double bonds aswell, where the point of substitution can be either at a carbon-carbontriple bond, a carbon-carbon double bond, or elsewhere in the group.Examples of alkyls include, but are not limited to methyl, ethyl,propyl, isobutyl. Examples of alkenyls include, but are not limited tovinyl, propenyl, allyl, methallyl, ethylidenyl norbornane, ethylidenenorbornyl, ethylidenyl norbornene, and ethylidene norbornenyl. Someexamples of alkynyls include, but are not limited to acetylenyl,propargyl, and methylacetylenyl,

As used herein, “aryl” includes any aromatic hydrocarbon from which onehydrogen atom has been removed; “aralkyl” includes any of theaforementioned alkyl groups in which one or more hydrogen atoms havebeen substituted by the same number of like and/or different aryl (asdefined herein) substituents; and “arenyl” includes any of theaforementioned aryl groups in which one or more hydrogen atoms have beensubstituted by the same number of like and/or different alkyl (asdefined herein) substituents. Some examples of aryls include, but arenot limited to phenyl and naphthalenyl. Examples of aralkyls include,but are not limited to benzyl and phenethyl, and some examples ofarenyls include, but are not limited to tolyl and xylyl.

As used herein, “cyclic alkyl”, “cyclic alkenyl”, and “cyclic alkynyl”also include bicyclic, tricyclic, and higher cyclic structures, as wellas the aforementioned cyclic structures further substituted with alkyl,alkenyl, and/or alkynyl groups. Representative examples include, but arenot limited to norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl,cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl,and cyclododecatrienyl, and the like.

Representative examples of X¹ include, but are not limited to methoxy,ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy,chloro, and acetoxy. Representative examples of X² and X³ include therepresentative examples listed above for X¹ as well as hydrogen, methyl,ethyl, propyl, isopropyl, sec-butyl, phenyl, vinyl, cyclohexyl, andhigher straight-chain alkyl, such as butyl, hexyl, octyl, lauryl, andoctadecyl, and the like.

Representative examples of R¹, R² and R³ include the terminalstraight-chain alkyls further substituted terminally at the other end,such as —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, and —CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—,and their beta-substituted analogs, such as —CH₂(CH₂)_(u)CH(CH₃)—, whereit is zero to 17; the structure derivable from methallyl chloride,—CH₂CH(CH₃)CH₂—; any of the structures derivable from divinylbenzene,such as —CH₂CH₂(C₆H₄)CH₂CH₂— and —CH₂CH₂(C₆H₄)CH(CH₃)—, where thenotation C₆H₄ denotes a disubstituted benzene ring, any of thestructures derivable from diallylether, such as —CH₂CH₂CH₂OCH₂CH₂CH₂—and —CH₂CH₂CH₂OCH₂CH(CH₃)—; any of the structures derivable frombutadiene, such as —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH(CH₃)—, and —CH₂CH(CH₂CH₃)—;any of the structures derivable from piperylene, such as—CH₂CH₂CH₂CH(CH₃)—, —CH₂CH₂CH(CH₂CH₃)—, and —CH₂CH(CH₂CH₂CH₃)—; any ofthe structures derivable from isoprene, such as —CH₂CH(CH₃)CH₂CH₂—,—CH₂CH(CH₃)CH(CH₃)—, —CH₂C(CH₃)(CH₂CH₃)—, —CH₂CH₂CH(CH₃)CH₂—,—CH₂CH₂C(CH₃)₂— and —CH₂CH[CH(CH₃)₂]—; any of the isomers of—CH₂CH₂-norbornyl-, —CH₂CH₂-cyclohexyl-; any of the diradicalsobtainable from norbornane, cyclohexane, cyclopentane,tetrahydrodicyclopetadiene, or cyclododecene by loss of two hydrogenatoms; the structures derivable from limonene,—CH₂CH(4-methyl-1-C₆H₉—)CH₃, where the notation C₆H₉ denotes isomers ofthe trisubstituted cyclohexane ring lacking substitution in the 2position; any of the monovinyl-containing structures derivable fromtrivinylcyclohexane, such as —CH₂CH₂(vinylC₆H₉)CH₂CH₂— and—CH₂CH₂(vinylC₆H₉)CH(CH₃)—, where the notation C₆H₉ denotes any isomerof the trisubstituted cyclohexane ring; any of the monounsaturatedstructures derivable from myrcene containing a trisubstituted C═C, suchas —CH₂CH[CH₂CH₂CH═C(CH₃)₂]CH₂CH₂—, —CH₂CH[CH₂CH₂CH═C(CH₃)₂]CH(CH₃)—,—CH₂C[CH₂CH₂CH═C(CH₃)₂](CH₂CH₃)—, —CH₂CH₂CH[CH₂CH₂CH═C(CH₃)₂]CH₂—,—CH₂CH₂(C—)(CH₃)[CH₂CH₂CH═C(CH₃)₂], and—CH₂CH[CH(CH₃)[CH₂CH₂CH═C(CH₃)₂]]—; and any of the monounsaturatedstructures derivable from myrcene lacking a trisubstituted C═C, such as—CH₂CH(CH═CH₂)CH₂CH₂CH₂C(CH₃)₂—, —CH₂CH(CH═CH₂)CH₂CH₂CH[CH(CH₃)₂]—,—CH₂C(═CH—CH₃)CH₂CH₂CH₂C(CH₃)₂—, —CH₂C(═CH—CH₃)CH₂CH₂CH[CH(CH₃)₂]—,—CH₂CH₂C(═CH₂)CH₂CH₂CH₂C(CH₃)₂—, —CH₂CH₂C (═CH₂)CH₂CH₂CH[CH(CH₃)₂]—,—CH₂CH═C(CH₃)₂CH₂CH₂CH₂C(CH₃)₂—, and —CH₂CH═C(CH₃)₂CH₂CH₂CH[CH(CH₃)₂].

Representative examples of G¹ include, but are not limited to,structures derivable from divinylbenzene, such as—CH₂CH₂(C₆H₄)CH(CH₂—)—, —CH₂CH₂(C₆H₃—)CH₂CH₂—, and—CH₂(CH—)(C₆H₄)CH(CH₂—)—, where the notation C₆H₄ denotes adisubstituted benzene ring and C₆H₃— denotes a trisubstituted ring; anystructures derivable from trivinylcyclohexane, such as—CH₂(CH—)(vinylC₆H₉)CH₂CH₂—; (—CH₂CH₂)₃C₆H₉, and (—CH₂CH₂)₂C₆H₉CH(CH₃)—,—CH₂(CH—)(vinylC₆H₉)(CH—)CH₂—, —CH₂CH₂C₆H₉[(CH—)CH₂—]₂,—CH(CH₃)C₆H₉[(CH—)CH₂—]₂, and C₆H₉[(CH—)CH₂—]₃, —CH₂(CH—)C₆H₉[CH₂CH₂—]₂,and —CH₂(CH—)C₆H₉[CH(CH₃)—][CH₂CH₂—], where the notation C₆H₉ denotesany isomer of the trisubstituted cyclohexane ring.

Representative examples of G² include, but are not limited to,structures derivable from divinylbenzene, such as —CH₂CH₂(C₆H₄)CH₂CH₂—,—CH₂CH₂(C₆H₄)CH(CH₂—)—,—CH₂CH₂(C₆H₃—)CH₂CH₂—, —CH₂(CH—)(C₆H₄)CH(CH₂—)—,where the notation C₆H₄ denotes a disubstituted benzene ring and C₆H₃—denotes a trisubstituted ring; any structures derivable fromtrivinylcyclohexane, such as —CH₂CH₂(vinylC₆H₉)CH₂CH₂—,(—CH₂CH₂)C₆H₉CH₂CH₃, —CH₂(CH—)(vinylC₆H₉)CH₂CH₂—, (—CH₂CH₂)₃C₆H₉,(—CH₂CH₂)₂C₆H₉CH(CH₃)—, —CH₂)(CH—)(vinylC₆H₉)(CH—)CH₂—,—CH₂CH₂C₆H₉[(CH—)CH₂—]₂, —CH(CH₃)C₆H₉[(CH—)CH₂—]₂, C₆H₉[(CH—)CH₂—]₃,—CH₂(CH—)C₆H₉[CH₂CH₂—]₂, and —CH₂(CH—)C₆H₉[CH(CH₃)—][CH₂CH₂—], where thenotation C₆H₉ denotes any isomer of the trisubstituted cyclohexane ring.

Representative examples of silated cyclic core polysulfide silanes ofthe present invention include any of the isomers of4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(1-methyl-5-triethoxysilyl-2-thiapentyl)-1,2-bis-(1-methyl-8-triethoxysilyl-2,3,4,5-tetrathiaoctyl)cyclohexane;4-(5-triethoxysilyl-3-thiapentyl)-1,2-bis-(8-triethoxysilyl-3,4,5,6-tetrathiaoctyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(12-triethoxysilyl-3,4,5,6-tetrathiadodecyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(11-triethoxysilyl-3,4,5,6-tetrathiaunidecyl)cyclohexane;4-(3-triethoxysilyl-1-thiapropyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6,7-pentathiatridecyl)cyclohexane;4-(6-diethoxymethylsilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(4-triethoxysilyl-2-thiabutyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(7-triethoxysilyl-3-thiaheptyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)cyclohexane;4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)benzene;4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)benzene;4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4-dithianonyl)benzene;bis-2-[4-(3-triethoxysilyl-2-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyltetrasulfide;bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyltrisulfide;bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyldisulfide;bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)phenyl]ethyltetrasulfide;bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)nathyl]ethyltetrasulfide;bis-2-[4-(4-diethoxymethylsilyl-2-thiabutyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)phenyl]ethyltrisulfide;bis-2-[4-(1-methyl-5-triethoxysilyl-2-thiapentyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cycloheptyl]ethyldisulfide;bis-2-[4-(4-triethoxysilyl-2-thiabutyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclooctyl]ethyldisulfide;bis-2-[4-(4-triethoxysilyl-2-thiabutyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclododecyl]ethyldisulfide,4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;and mixtures thereof.

In another embodiment of the present invention the Formulae (1), (2) and(3), are described wherein each occurrence of R¹ and R³ areindependently selected from a divalent hydrocarbon fragment having from1 to about 5 carbon atoms that include branched and straight chainalkyl, alkenyl, alkynyl, aryl or aralkyl groups in which one hydrogenatom was substituted with a Y¹ or Y² group; each occurrence of Y¹ and Y²is chosen independently from silyl (—SiX¹,X²,X³); each occurrence of R²is a straight chain hydrocarbon represented by —(CH₂)_(f)— where f is aninteger from about 0 to about 5; each occurrence of R⁴ is chosenindependently from a polyvalent cyclic hydrocarbon fragment of 5 toabout 12 carbon atoms that was obtained by substitution of hydrogenatoms equal to the sum of a+c+e, and include cyclic alkyl or aryl inwhich a+c+e−1 hydrogens have been replaced; each occurrence of R⁵ ischosen independently from a polyvalent hydrocarbon fragment of 5 toabout 12 carbon atoms that was obtained by substitution of hydrogenatoms equal to the sum of c+e, and include branched and straight chainalkyl, alkenyl, alkynyl, aryl and aralkyl groups in which c+e−1hydrogens have been replaced; each occurrence of X¹ is chosenindependently from f hydrolysable groups selected from —OH, and —OR⁶, inwhich R⁶ is any monovalent hydrocarbon group having from 1 to 5 carbonatoms, and includes branched or straight chain alkyl, alkenyl, aryl oraralkyl groups; each occurrence of X² and X³ is chosen independentlytaken from R⁶ as defined for this embodiment and, any of X¹ as definedfor this embodiment, and —OSi containing groups that result from thecondensation of silanols; each occurrence of the subscripts, a, b, c, d,e, f, m, n, o, p, and x, is independently given by a is 1 to about 2; bis 1 to about 3; c is 1; d is 1 to about 3; e is 1; f is 0 to about 5; mis 1, n is 1 to about 10; o is 0 to about 1; p is 1, and x is 1 to about6.

According to another embodiment of the present invention, 30 to 99weight percent of the silated core polysulfide of the filler compositionof the present invention is blended with 70 to 1 weight percent ofanother silane, including silanes of the structure represented inFormula (4)[X¹X²X³SiR¹S_(x)R³SiX¹X²X³]  (4)wherein each occurrence of each occurrence of R¹ and R³ are chosenindependently from a divalent hydrocarbon fragment having from 1 toabout 20 carbon atoms that include branched and straight chain alkyl,alkenyl, alkynyl, aryl or aralkyl groups in which one hydrogen atom wassubstituted with a silyl group, (—SiX¹X²X³), wherein X¹ is chosenindependently from any of hydrolysable groups selected from —Cl, —Br,—OH, —OR⁶, and R⁶C(═O)O—, in which R⁶ is any monovalent hydrocarbongroup having from 1 to 20 carbon atoms, and includes branched orstraight chain alkyl, alkenyl, aryl or aralkyl group and X² and X³ isindependently taken from hydrogen, R⁶ as defined for this embodiment,any of X¹ as defined above, and —OSi containing groups that result fromthe condensation of silanols. This mixture of the silated corepolysulfide of Formula (1) and the other silanes of Formula (4)correspond to a weight ratio about 0.43 to 99. In another embodiment,the mixture of the silated core polysulfide of Formula (1) and the othersilanes of Formula (4) are in a weight ratio of about 1 to 19.

Representative examples of this silane described by Formula (4) arelisted in U.S. Pat. No. 3,842,111, which is incorporated herein byreference, and include bis-(3-triethoxysilylpropyl)disulfide;bis-(3-triethoxysilylpropyl)trisulfide;bis-(3-triethoxysilylpropyl)tetrasulfide;bis(3-triethoxysilylpropyl)pentasulfide;bis-(3-diethoyxmethylsilypropyl)disulfide; bis-triethoxysilylmethyldisulfide; bis-(4-triethoxysilylbenzyl)disulfide;bis-(3-triethoxysilylphenyl)disulfide; and the like.

The bonding of sulfur to a methylene group on R⁴ and R⁵ is desiredbecause the methylene group mitigates excessive steric interactionsbetween the silane and the filler and polymer. Two successive methylenegroups mitigate steric interactions even further and also addflexibility to the chemical structure of the silane, thereby enhancingits ability to accommodate the positional and orientational constraintsimposed by the morphologies of the surfaces of both the rubber andfiller at the interphase, at the molecular level. The silane flexibilitybecomes increasingly important as the total number of silicon and sulfuratoms bound to G¹ and G² increases from 3 to 4 and beyond. Structures inwhich the polysulfide group is bonded directly to secondary and tertiarycarbon atoms, ring structures, especially aromatic structures, are rigidand sterically hindered. The accelerators and curatives cannot readilyorient themselves with the polysulfide group to affect reaction and thesilated core polysulfide cannot readily orient itself to meet availablebinding sites on silica and polymer. This would tend to leave sulfurgroups unbound to polymer, thereby reducing the efficiency by which theprinciple of multiple bonding of silane to polymer via multiple sulfurgroups on silane, is realized.

The use of a sulfide group to attach the silyl group to the core,—S—R²SiX¹X²X³, provides a convenient and cost effective way to bond thesilyl group to the core. The sulfide group is less reactive than thepolysulfide groups of the present invention and therefore is less likelyto be broken during the curing of the rubbers containing the silated 1scyclic core polysulfides. The sulfide linkage of the silyl group to thecore also makes it easier synthesize molecules with different lengths ofthe R² relative to R¹ and R³ and therefore to optimize the chemicalstructure of the silated cyclic core polysulfides to achieve bondingbetween the inorganic filler, such as silica, and the rubber.

The function of the other silanes in the filler is to occupy sites onthe surface of the silica which aid in dispersing the silica andcoupling with the polymer.

Fillers of the present invention can be used as carriers for liquidsilanes and reinforcing fillers for elastomers in which the silated corepolysulfide is capable of reacting or bonding with the surface of theelastomers. The fillers that are used as carrier should be non-reactivewith the silated core polysulfide. The non-reactive nature of thefillers is demonstrated by ability of the silated core polysulfide to beextracted at greater than 50 percent of the loaded silane using anorganic solvent. The extraction procedure is given in U.S. Pat. No.6,005,027, which is incorporated herein by reference. Carriers include,but are not limited to, porous organic polymers, carbon black,diatomaceous earth, and silicas that are characterized by relatively lowdifferential of less than 1.3 between the infrared absorbance at 3502cm⁻² of the silica when taken at 105° C. and when taken at 500° C., asdescribed in U.S. Pat. No. 6,005,027. In one embodiment, the amount ofsilated core polysulfide and, optionally, the other silanes of Formula(4) that can be loaded on the carrier is between 0.1 and 70 percent byweight. In another embodiment, the silated core polysulfide and,optionally, the other silanes of Formula (4) can be loaded on thecarrier at concentrations between 10 and 50 percent by weight In yetanother embodiment, the filler is a particulate filler.

Reinforcing fillers useful in the present invention include fillers inwhich the silanes are reactive with the surface of the filler.Representative examples of the fillers include, but are not limited to,inorganic fillers, siliceous fillers, metal oxides such as silica(pyrogenic and/or precipitated), titanium, aluminosilicate and alumina,clays and talc, and the like. Particulate, precipitated silica is usefulfor such purpose, particularly when the silica has reactive surfacesilanols. In one embodiment of the present invention, a combination of0.1 to 20 percent silated core polysulfide and optionally, the othersilanes of Formula (4) and 80 to 99.9 percent silica or otherreinforcing fillers is utilized to reinforce various rubber products,including treads for tires. In another embodiment, a filler iscomprising from about 0.5 to about 10 percent silated core polysulfideof Formula (1) and optionally a second silane of Formula (4) and about90 to about 99.5 weight percent particulate filler. In anotherembodiment of the present invention, alumina can be used alone with thesilated core polysulfide, or in combination with silica and the silatedcore polysulfide. The term, alumina, can be described herein as aluminumoxide, or Al₂O₃. In a further embodiment of the present invention, thefillers may be in the hydrated form.

Mercury porosity surface area is the specific surface area determined bymercury porosimetry. Using this method, mercury is penetrated into thepores of the sample after a thermal treatment to remove volatiles. Setup conditions may be suitably described as using about a 100 mg sample;removing volatiles during about 2 hours at about 150° C. and ambientatmospheric pressure; ambient to about 2000 bars pressure measuringrange. Such evaluation may be performed according to the methoddescribed in Winslow, Shapiro in ASTM bulletin, p. 39 (1959) oraccording to DIN 66133. For such an evaluation, a CARLO-ERBA Porosimeter2000 might be used. The average mercury porosity specific surface areafor the silica should be in a range of about 100 to about 300 m²/g

The pore size distribution for the silica, alumina and aluminosilicateaccording to such mercury porosity evaluation is considered herein to besuch that five percent or less of its pores have a diameter of less thanabout 10 nm, about 60 to about 90 percent of its pores have a diameterof about 10 to about 100 nm, about 10 to about 30 percent of its poreshave a diameter at about 100 to about 1,000 nm, and about 5 to about 20percent of its pores have a diameter of greater than about 1,000 nm.

Silica might be expected to have an average ultimate particle size, forexample, in the range of about 10 to about 50 nm as determined by theelectron microscope, although the silica particles may be even smaller,or possibly larger, in size. Various commercially available silicas maybe considered for use in this invention such as, from PPG Industriesunder the HI-SIL trademark with designations HI-SIL 210, 243, etc.;silicas available from Rhone-Poulenc, with, for example, designation ofZEOSIL 1165MP; silicas available from Degussa with, for example,designations VN2 and VN3, etc. and silicas commercially available fromHuber having, for example, a designation of HUBERSIL7 8745.

In one embodiment of the invention, the filler compositions may utilizethe silated cyclic core polysulfide with fillers such as silica, aluminaand/or aluminosilicates in combination with carbon black reinforcingpigments. In another embodiment of the invention, the fillercompositions may comprise a particulate filler mix of about 15 to about95 weight percent of the siliceous filler, and about 5 to about 85weight percent carbon black, and 0.1 to about 19 weight percent ofsilated cyclic core polysulfide, wherein the carbon black has a CTABvalue in a range of about 80 to about 150. In yet another embodiment ofthe invention, it is desirable to use a weight ratio of siliceousfillers to carbon black of at least about 3 to 1. In yet anotherembodiment, a weight ratio of siliceous fillers to carbon black of atleast about 10 to 1. In still another embodiment of the presentinvention, the weight ratio of siliceous fillers to carbon black mayrange from about 3 to 1 to about 30 to 1.

In one embodiment of the invention, the filler can be comprised of about60 to about 95 weight percent of silica, alumina and/or aluminosilicateand, correspondingly, about 40 to about 5 weight percent carbon blackand from about 0.1 to 20 weight percent silated cyclic core polysulfideof the present invention and optionally a second silane, with theproviso that the mixture of the components add up to 100 percent. Thesiliceous filler and carbon black may be pre-blended or blended togetherin the manufacture of the vulcanized rubber.

The filler can be essentially inert to the silane with which it isadmixed as is the case with carbon black or organic polymers, or it canbe reactive therewith, e.g., the case with carriers possessing metalhydroxyl surface functionality, egg., silicas and other siliceousparticulates which possess surface silanol functionality.

According to yet another embodiment of the present invention, a rubbercomposition, such as for use in tires is provided comprising;

-   -   (a) a rubber component;    -   (b) a free-flowing filler composition with a silated cyclic core        polysulfide of Formula (1);    -   (c) and, optionally a second silane, such as silanes according        to Formula (4).

The silated cyclic core polysulfide silane(s) and optionally othersilane coupling agents may be premixed or pre-reacted with the fillerparticles prior to the addition to the rubber mix, or added to a rubbermix during the rubber and filler processing, or mixing stages. If thesilated cyclic core polysulfide silanes and, optionally, other silanesand filler are added separately to the rubber mix during the rubber andfiller mixing, or processing stage, it is considered that the silatedcyclic core polysulfide silane(s) then combine(s) in an in-situ fashionwith the filler.

In accordance with another embodiment of the present invention anuncured or cured rubber composition, such as for use in tires, isprovided comprising:

-   -   (a) a rubber component;    -   (b) a free-flowing filler composition with a silated cyclic core        polysulfide of Formula (1)    -   (c)optionally, silanes, such as silanes of Formula (4);    -   (d) curatives; and    -   (e) optionally, other additives.

The rubbers useful with the filler compositions of the present inventioninclude sulfur vulcanizable rubbers including conjugated dienehomopolymers and copolymers, and copolymers of at least one conjugateddiene and aromatic vinyl compound. Suitable organic polymers forpreparation of rubber compositions are well known in the art and aredescribed in various textbooks including The Vanderbilt Rubber Handbook,Ohm, R. F., R. T. Vanderbilt Company, Inc., 1990 and in the Manual forthe Rubber Industry, Kemperman, T and Koch, S. Jr., Bayer A G,LeverKusen, 1993, the disclosures of which are incorporated by referenceherein in their entireties.

In one embodiment of the present invention, the polymer for use hereinis solution-prepared styrene-butadiene rubber (SSBR). In anotherembodiment of the invention, the solution prepared SSBR typically has abound styrene content in a range of about 5 to about 50 percent, andabout 9 to about 36 percent in another embodiment. According to anotherembodiment of the present invention, the polymer may be selected fromthe group consisting of emulsion-prepared styrene-butadiene rubber(ESBR), natural rubber (NR), ethylene-propylene copolymers andterpolymers (EP, EPDM), acrylonitrile-butadiene rubber (NBR),polybutadiene (BR), and the like, and mixtures thereof.

In one embodiment, the rubber composition is comprised of at least onediene-based elastomer, or rubber. Suitable conjugated dienes include,but are not limited to, isoprene and 1,3-butadiene and suitable vinylaromatic compounds include, but are not limited to, styrene and alphamethyl styrene. Polybutadiene may be characterized as existingprimarily, typically about 90% by weight, in the cis-1,4-butadiene form,but other compositions may also be used for the purposes describedherein.

Thus, the rubber is a sulfur curable rubber. Such diene based elastomer,or rubber, may be selected, for example, from at least one ofcis-1,4-polyisoprene rubber (natural and/or synthetic), emulsionpolymerization prepared styrene/butadiene copolymer rubber, organicsolution polymerization prepared styrene/butadiene rubber,3,4-polyisoprene rubber, isoprene/butadiene rubber,styrene/isoprene/butadiene terpolymer rubber, cis-1,4-polybutadiene,medium vinyl polybutadiene rubber (35-50 percent vinyl), high vinylpolybutadiene rubber (50-75 percent vinyl), styrene/isoprene copolymers,emulsion polymerization prepared styrene/butadiene/acrylonitrileterpolymer rubber and butadiene/acrylonitrile copolymer rubber. For someapplications, an emulsion polymerization derived styrene/butadiene(ESBR) having a relatively conventional styrene content of about 20 to28 percent bound styrene, or an ESBR having a medium to relatively highbound styrene content of about 30 to 45 percent may be used.

Emulsion polymerization prepared styrene/butadiene/acrylonitrileterpolymer rubbers containing 2 to 40 weight percent bound acrylonitrilein the terpolymer are also contemplated as diene based rubbers for usein this invention.

The vulcanized rubber composition should contain a sufficient amount offiller composition to contribute a reasonably high modulus and highresistance to tear. In one embodiment of the present invention, thecombined weight of the filler composition may be as low as about 5 toabout 120 parts per hundred parts (phr), or about 5 to about 100 phr. Inanother embodiment, the combined weight of the filler composition isfrom about 25 to about 85 phr and at least one precipitated silica isutilized as a filler in another embodiment. The silica may becharacterized by having a BET surface area, as measured using nitrogengas, in the range of about 40 to about 600 m²/g. In one embodiment ofthe invention, the silica has a BET surface area in a range of about 50to about 300 m²/g. The BET method of measuring surface area is describedin the Journal of the American Chemical Society, Volume 60, page 304(1930). The silica typically may also be characterized by having adibutylphthalate (DBP) absorption value in a range of about 100 to about350, and more usually about 150 to about 300. Further, the silica, aswell as the aforesaid alumina and aluminosilicate, may be expected tohave a CTAB surface area in a range of about 100 to about 220. The CTABsurface area is the external surface area as evaluated by cetyltrimethylammonium bromide with a pH of about 9. The method is describedin ASTM D 3849.

The rubber compositions of the present invention may be prepared bymixing one or more of the silated cyclic core polysulfide silanes andoptionally other silanes with the organic polymer before, during orafter the compounding of the filler composition into the organicpolymer. The silated cyclic core polysulfide silanes and optionallyother silanes also may be added before or during the compounding of thefiller composition into the organic polymer, because these silanesfacilitate and improve the dispersion of the filler. In anotherembodiment, the total amount of silated cyclic core polysulfide silanepresent in the resulting combination should be about 0.05 to about 25parts by weight per hundred parts by weight of organic polymer (phr);and 1 to 10 phr in another embodiment. In yet another embodiment,fillers can be used in quantities ranging from about 5 to about 120 phr,about 5 to about 100 phr, or about 25 to about 80 phr, and still inanother embodiment from about 25 to about 110, or about 25 to about 105.

In practice, sulfur vulcanized rubber products typically are prepared bythermomechanically mixing rubber and various ingredients in asequentially step-wise manner followed by shaping and curing thecompounded rubber to form a vulcanized product. First, for the aforesaidmixing of the rubber and various ingredients, typically exclusive ofsulfur and sulfur vulcanization accelerators (collectively, curingagents), the rubber(s) and various rubber compounding ingredientstypically are blended in at least one, and often (in the case of silicafilled low rolling resistance tires) two or more, preparatorythermomechanical mixing stage(s) in suitable mixers. Such preparatorymixing is referred to as nonproductive mixing or non-productive mixingsteps or stages. Such preparatory mixing usually is conducted attemperatures of about 140° C. to about 200° C., and for somecompositions, about 150° C. to about 170° C. Subsequent to suchpreparatory mix stages, in a final mixing stage, sometimes referred toas a productive mix stage, curing agents, and possibly one or moreadditional ingredients, are mixed with the rubber compound orcomposition, at lower temperatures of typically about 50° C. to about130° C. in order to prevent or retard premature curing of the sulfurcurable rubber, sometimes referred to as scorching. The rubber mixture,also referred to as a rubber compound or composition, typically isallowed to cool, sometimes after or during a process intermediate millmixing, between the aforesaid various mixing steps, for example, to atemperature of about 50° C. or lower. When it is desired to mold and tocure the rubber, the rubber is placed into the appropriate mold at atemperature of at least about 130° C. and up to about 200° C. which willcause the vulcanization of the rubber by the S—S bond-containing groups(i.e., disulfide, trisulfide, tetrasulfide, etc.; polysulfide) on thesilated core polysulfide silanes and any other free sulfur sources inthe rubber mixture.

Thermomechanical mixing refers to the phenomenon whereby under the highshear conditions in a rubber mixer, the shear forces and associatedfriction occurring as a result of mixing the rubber compound, or someblend of the rubber compound itself and rubber compounding ingredientsin the high shear mixer, the temperature autogeneously increases, i.e.it “heats up”. Several chemical reactions may occur at various steps inthe mixing and curing processes.

The first reaction is a relatively fast reaction and is consideredherein to take place between the filler and the silicon alkoxide groupof the silated cyclic core polysulfides. Such reaction may occur at arelatively low temperature such as, for example, at about 120° C. Thesecond reaction is considered herein to be the reaction which takesplace between the sulfur-containing portion of the silated cyclic corepolysulfide silane, and the sulfur vulcanizable rubber at a highertemperature; for example, above about 140° C.

Another sulfur source may be used, for example, in the form of elementalsulfur, such as but not limited to S₈. A sulfur donor is consideredherein as a sulfur containing compound which liberates free, orelemental sulfur, at a temperature in a range of about 140° C. to about190° C. Such sulfur donors may be, for example, although are not limitedto, polysulfide vulcanization accelerators and organosilane polysulfideswith at least two connecting sulfur atoms in its polysulfide bridge. Theamount of free sulfur source addition to the mixture can be controlledor manipulated as a matter of choice relatively independently from theaddition of the aforesaid silated cyclic core polysulfide silane. Thus,for example, the independent addition of a sulfur source may bemanipulated by the amount of addition thereof and by the sequence ofaddition relative to the addition of other ingredients to the rubbermixture.

In one embodiment of the invention, the rubber composition may thereforecomprise about 100 parts by weight rubber (phr) of at least one sulfurvulcanizable rubber selected from the group consisting of conjugateddiene homopolymers and copolymers, and copolymers of at least oneconjugated diene and aromatic vinyl compound, about 5 to 100 phr,preferably about 25 to 80 phr of at least one filler, up to about 5 phrcuring agent, and about 0.05 to about 25 phr of at least one silatedcyclic core polysulfide silane as described in the present invention.

In another embodiment, the filler composition comprises from about 1 toabout 85 weight percent carbon black based on the total weight of thefiller composition and up to about 20 parts by weight of at least onecyclic silated core polysulfide silane of the present invention based onthe total weight of the filler composition, including about 2 to about20 parts by weight of at least one cyclic silated core polysulfidesilane of the present invention based on the total weight of the fillercomposition.

The rubber composition may be prepared by first blending rubber, fillerand silated cyclic core polysulfide silane or rubber, filler pretreatedwith all or a portion of the silated cyclic core polysulfide silane andany remaining silated cyclic core polysulfide silane, in a firstthermomechanical mixing step to a temperature of about 140° C. to about200° C. for about 2 to about 20 minutes. The fillers may be pretreatedwith all or a portion of the silated core polysulfide silane and anyremaining silated cyclic core polysulfide silane, in a firstthermomechanical mixing step to a temperature of about 140° C. to about200° C. for about 4 to 15 minutes. Optionally, the curing agent is thenadded in another thermomechanical mixing step at a temperature of about50° C. and mixed for about 1 to about 30 minutes. The temperature isthen heated again to between about 130° C. and about 200° C. and curingis accomplished in about 5 to about 60 minutes.

In another embodiment of the present invention, the process may alsocomprise the additional steps of preparing an assembly of a tire orsulfur vulcanizable rubber with a tread comprised of the rubbercomposition prepared according to this invention and vulcanizing theassembly at a temperature in a range of about 130° C. to about 200° C.

Other optional ingredients may be added in the rubber compositions ofthe present invention including curing aids, i.e. sulfur compounds,including activators, retarders and accelerators, processing additivessuch as oils, plasticizers, tackifying resins, silicas, other fillers,pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants,peptizing agents, reinforcing materials such as, for example, carbonblack, and so forth. Such additives are selected based upon the intendeduse and on the sulfur vulcanizable material selected for use, and suchselection is within the knowledge of one of skill in the art, as are therequired amounts of such additives known to one of skill in the art.

The vulcanization may be conducted in the presence of additional sulfurvulcanizing agents. Examples of suitable sulfur vulcanizing agentsinclude, for example elemental sulfur (free sulfur) or sulfur donatingvulcanizing agents, for example, an amino disulfide, polymericpolysulfide or sulfur olefin adducts which are conventionally added inthe final, productive, rubber composition mixing step. The sulfurvulcanizing agents, which are common in the art are used, or added inthe productive mixing stage, in an amount ranging from about 0.4 toabout 3 phr, or even, in some circumstances, up to about 8 phr, with arange of from about 1.5 to about 2.5 phr and all subranges therebetweenin one embodiment from 2 to about 2.5 phr and all subranges therebetweenin another embodiment.

Optionally, vulcanization accelerators, i.e., additional sulfur donors,may be used herein. It is appreciated that may include the followingexamples, benzothiazole, alkyl thiuram disulfide, guanidine derivativesand thiocarbamates. Representative of such accelerators can be, but notlimited to, mercapto benzothiazole (MBT), tetramethyl thiuramdisulfide(TMTD), tetramethyl thiuram monosulfide (TMTM), benzothiazoledisulfide (MBTS), diphenylguanidine (DPG), zinc dithiocarbamate (ZBEC),alkylphenoldisulfide, zinc iso-propyl xanthate (ZIX),N-dicyclohexyl-2-benzothiazolesulfenamide (DCBS),N-cyclohexyl-2-benzothiazolesulfenamide (CBS),N-tert-buyl-2-benzothiazolesulfenamide (TBBS),N-tert-buyl-2-benzothiazolesulfenimide (TBSI), tetrabenzylthiuramdisulfide (TBzTD), tetraethylthiuram disulfide (TETD),N-oxydiethylenebenzothiazole-2-sulfenamide, N,N-diphenylthiourea,dithiocarbamylsulfenamide, N,N-diisopropylbenzothiozole-2-sulfenamide,zinc-2-mercaptotoluimidazole, dithiobis(N-methyl piperazine),dithiobis(N-beta-hydroxy ethyl piperazine) and dithiobis(dibenzylamine). Other additional sulfur donors, may be, for example, thiuram andmorpholine derivatives. Representative of such donors are, for example,but not limited to, dimorpholine disulfide, dimorpholine tetrasulfide,tetramethyl thiuram tetrasulfide, benzothiazyl-2,N-dithiomorpholide,thioplasts, dipentamethylenethiuram hexasulfide, anddisulfidecaprolactam.

Accelerators are used to control the time and/or temperature requiredfor vulcanization and to improve the properties of the vulcanizate. Inone embodiment, a single accelerator system may be used, i.e., a primaryaccelerator. Conventionally, a primary accelerator(s) is used in totalamounts ranging from about 0.5 to about 4 phr and all subrangestherebetween in one embodiment, and from about 0.8 to about 1.5, phr andall subranges therebetween in another embodiment. Combinations of aprimary and a secondary accelerator might be used with the secondaryaccelerator being used in smaller amounts (of about 0.05 to about 3 phrand all subranges therebetween) in order to activate and to improve theproperties of the vulcanizate. Delayed action accelerators may be used.Vulcanization retarders might also be used. Suitable types ofaccelerators are amines, disulfides, guanidines, thioureas, thiazoles,thiurams, sulfenamides, dithiocarbamates and xanthates. In oneembodiment, the primary accelerator is a sulfenamide. If a secondaryaccelerator is used, the secondary accelerator can be a guanidine,dithiocarbamate and/or thiuram compounds. Preferably, tetrabenzylthiuramdisulfide is utilized as a secondary accelerator in combination withN-tert-buyl-2-benzothiazolesulfenamide with or withoutdiphenylguanidine. Tetrabenzylthiuram disulfide is a preferredaccelerator as it does not lead to the production of nitrosating agents,such as, for example, tetramethylthiuram disulfide.

Typical amounts of tackifier resins, if used, comprise about 0.5 toabout 10 phr and all subranges therebetween, usually about 1 to about 5phr and all subranges therebetween. Typical amounts of processing aidscomprise about 1 to about 50 phr and all subranges therebetween. Suchprocessing aids can include, for example, aromatic, napthenic, and/orparaffinic processing oils. Typical amounts of antioxidants compriseabout 1 to about 5 phr. Representative antioxidants may be, for example,diphenyl-p-phenylenediamine and others, such as, for example, thosedisclosed in the Vanderbilt Rubber Handbook (1978), pages 344-346.Typical amounts of antiozonants, comprise about 1 to about 5 phr and allsubranges therebetween. Typical amounts of fatty acids, if used, whichcan include stearic acid, comprise about 0.5 to about 3 phr and allsubranges therebetween. Typical amounts of zinc oxide comprise about 2to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phrand all subranges therebetween. Often microcrystalline waxes are used.Typical amounts of peptizers comprise about 0.1 to about 1 phr and allsubranges therebetween. Typical peptizers may be, for example,pentachlorothiophenol and dibenzamidodiphenyl disulfide.

The rubber compositions of this invention can be used for variouspurposes. For example, it can be used for various tire compounds,weather stripping, and shoe soles. In one embodiment of the presentinvention, the rubber compositions described herein are particularlyuseful in tire treads, but may also be used for all other parts of thetire as well. The tires can be built, shaped, molded and cured byvarious methods which are known and will be readily apparent to thosehaving skill in such art.

Preferred compositions include those compositions useful for themanufacture of tires or tire components, including vehicle tires, andinclude rubber compositions that include at least one vulcanizablerubber and at least one preformed filler. The fillers included in thepreformed filler can include, by way of nonlimiting example, carbonblacks, silicas, silicon based fillers, and metal oxides present eitheralone or in combinations. For example, an active filler may be selectedfrom the group described above (e.g., carbon blacks, silicas, siliconbased fillers, and metal oxides) and may be, but does not have to be,present in a combined amount of at least 35 parts by weight per 100parts by weight of total vulcanizable rubber, of which at least 10 partscan be carbon black, silica, or some combination thereof, and whereinsaid compositions can be formulated so that they are vulcanizable toform a tire component compound. The tire component compounds may have aShore A Hardness of not less than 40 and not greater than 95 and aglass-transition temperature Tg (E″_(max)) not less than −80° C. and notgreater than 0° C. The Shore A Hardness is measured in accordance withDIN 53505. The glass-transition temperature Tg (E″_(max)) is measured inaccordance with DIN 53513 with a specified temperature sweep of −80° C.to +80° C. and a specified compression of 10±0.2% at 10 Hz. Preferably,the rubber comprises vulcanizable rubbers selected from natural rubbers,synthetic polyisoprene rubbers, polyisobutylene rubbers, polybutadienerubbers, random styrene-butadiene rubbers (SBR), and mixtures thereof.Moreover, an active filler includes a filler that is interactive withthe rubber or tire composition and itself, and changes properties of therubber or tire composition.

All references cited are specifically incorporated herein by referenceas they are relevant to the present invention.

EXAMPLES

The examples presented below demonstrate significant advantages ofsilated cyclic core polysulfides described herein relative those of thecurrently practiced art, and their performance as coupling agents insilica-filled rubber.

Example 1 Preparation of (6-triethoxysilyl-3-thia-1-hexyl)-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane, related oliogmers andbis-(3-triethoxysilylpropyl)polysulfide mixture

This example illustrates the preparation of a silated cyclic coredisulfide from a core containing three vinyl groups through theformation of an intermediate thioacetate silane. Thetris-(4-oxo-3-thiapentyl)cyclohexane was prepared by the reaction ofthioacetic acid with trivinylcyclohexane. Into a 5 L, three-neck roundbottomed flask equipped with magnetic stir bar, temperatureprobe/controller, heating mantle, addition funnel, condenser, and airinlet were charged 1,2,4-trivinylcyclohexane (779 grams, 4.8 moles) andt-butyl peroxide (8.0 grams, 0.055 mole). Freshly distilled thioaceticacid (1297 grams, 16.8 moles) was added by means of an addition funnelover a period of 30 minutes. The temperature rose from room temperatureto 59° C. The reaction mixture was allowed to cool to room temperature,tert-butyl peroxide (25.3 grams, 0.173 moles) was added in twoincrements and the reaction mixture was heated overnight at 75° C. Aftercooling to 42° C., air was bubbled into the reaction mixture and anexotherm was observed. The mixture was stirred overnight at 75° C. andthen cooled to room temperature. The reaction mixture was stripped toremove any low boiling species under reduced pressure and a maximumtemperature of 135° C. to give the final product (1,866 grams, 4.77moles). The yield was 99 percent.

The 1,2,4-tris-(2-mercaptoethyl)cyclohexane was prepared by removing theacyl group. Into a 5 L, three-neck round bottomed flask equipped withmagnetic stir bar, temperature probe/controller, heating mantle,addition funnel, distilling head and condenser, and nitrogen inlet werecharged tris-(4-oxo-3-thiapentyl)cyclohexane (1,866 grams, 4.77 moles)and absolute ethanol (1,219 grams, 26.5 moles). Sodium ethoxide inethanol (99 grams of 21% sodium ethoxide, purchased from AldrichChemical) was added in five increments. The mixture was heated and theethanol and ethyl acetate were removed. Ethanol (785 grams) was addedand the ethyl acetate and ethanol were distilled from the mixture atatmospheric pressure. Ethanol (1,022 grams) was added to the mixture andthe ethyl acetate, ethanol and low boiling components were distilledform the mixture under reduced pressure at 73° C. The mercaptanintermediate (1,161 grams, 4.5 moles) was used in the next step for thesynthesis. The yield was 93 percent.

The bis-(2-mercaptoethyl)(6-triethylsilyl-3-thia-1-hexyl)cyclohexane wasprepared by reaction of the trimercaptan intermediate with3-chloropropyltriethyoxysilane. Into a 3 L, three-neck round bottomedflask equipped with magnetic stir bar, temperature probe/controller,heating mantle, addition funnel, condenser, air inlet and a sodiumhydroxide scrubber, was charged 1,2,4-tris-(2-mercaptoethyl)cyclohexane(450 grams, 1.7 moles). Sodium ethoxide in ethanol (421 grams of 21%sodium ethoxide, purchased from Aldrich Chemical) was added over twohours. 3-Chloropropyltriethoxysilane (410 grams, 1.7 moles) was addedslowly over a period of 2 hours and then heated at reflux for 14 hours.An additional aliquot of 3-chloropropyltriethoxysilane (42.5 grams, 0.18mole) was added, heated for 2.5 hours at 79° C., cooled and thenfiltered. The crude product was distilled under reduced pressure. Thefraction that boiled between 191 and 215° C. was collected (343 grams,0.73 mole) and used in the next step of the synthesis. The product yieldwas 43 percent.

The product,(6-triethoxysilyl-3-thia-1-hexyl)-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane,was prepared by reacting the silated dimercaptan intermediated withsulfur and 3-chloropropyltriethoxysilane. Into a 3 L, three-neck roundbottomed flask equipped with magnetic stir bar, temperatureprobe/controller, heating mantle, addition funnel, distilling head andcondenser, and nitrogen inlet were chargedbis-(2-mercaptoethyl)(6-triethylsilyl-3-thia-1-hexyl)cyclohexane (326grams, 0.7 mole), sodium ethoxide in ethanol (451 grams of 21% sodiumethoxide, purchased from Aldrich Chemical), sulfur powder (45 grams, 1.4moles) and absolute ethanol (352 grams) and refluxed for 3 hours.3-Chloropropyltriethoxysilane (336 grams, 1.4 moles) was added, refluxedfor 72 hours, cooled and filtered using a glass fritted filter with a25-50 micron pore size. The solids were washed with toluene, the organiclayers combined and stripped to remove the lights. The final product(635 grams, 0.7 mole) was analyzed by HPLC. The chromatograph, shown inFIG. 1, indicated a mixture of monomeric and oligomeric products.

One isomer of(6-triethoxysilyl-3-thia-1-hexyl)-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexanehas the following structure:

Example 2 Preparation of(6-triethoxysilyl-3-thia-1-hexyl)-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane,related oliogmers and bis-(3-triethoxysilylpropyl)polysulfide mixture

The dimercaptan silane intermediate,(6-triethoxysilyl-3-thia-1-hexyl)-bis-(2-mercaptoethyl)cyclohexane, wasprepared by the procedure described in Example 1.

The product,(6-triethoxysilyl-3-thia-1-hexyl)-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane,related oliogmers and bis-(3-triethoxysilylpropyl)polysulfide mixture,was prepared by reacting the dimercaptan silane with base, sulfur and3-chloropropyltriethoxysilane. Into a 2 L, three-neck round bottomedflask equipped with magnetic stir bar, temperature probe/controller,heating mantle, addition funnel, distilling head and condenser, andnitrogen inlet were charged bis-(2-mercaptoethyl)(6-triethylsilyl-3-thia-1-hexyl)cyclohexane (249.7 grams 0.53 mole), sodium ethoxide inethanol (345.2 grains of 21% sodium ethoxide, purchased from AldrichChemical), sulfur powder (102.5 grams, 3.2 moles) and absolute ethanol(250 grams) and refluxed for 24 hours. 3-Chloropropyltriethoxysilane(256.5 grams, 1.07 moles) was added, refluxed for 72 hours, cooled andthen filtered using a 3.5 micron asbestocel filter. The final product(487.4 grams, 0.47 mole, 88 percent yield) was analyzed by HPLC. Thechromatograph indicated a mixture of products.

One isomer of(6-triethoxysilyl-3-thia-1-hexyl)-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexanehas the following structure;

Comparative Example A-C, Examples 3-5 The Use of Silanes in Low RollingResistant Tire Tread Formulation

A model low rolling resistance passenger tire tread formulation asdescribed in Table 1 and a mix procedure were used to evaluaterepresentative examples of the silanes of the present invention. Thesilane in Example 2 was mixed as follows in a “B” BANBURY® (FarrellCorp.) mixer with a 103 cu. in. (1,690 cc) chamber volume. The mixing ofthe rubber was done in two steps. The mixer was turned on with the mixerat 80 rpm and the cooling water at 71° C. The rubber polymers were addedto the mixer and ram down mixed for 30 seconds. The silica and the otheringredients in Masterbatch of Table 1 except for the silane and the oilswere added to the mixer and ram down mixed for 60 seconds. The mixerspeed was reduced to 35 rpm and then the silane and oils of theMasterbatch were added to the mixer and ram down for 60 seconds. Themixer throat was dusted down and the ingredients ram down mixed untilthe temperature reached 149° C. The ingredients were then mixed for anaddition 3 minutes and 30 seconds. The mixer speed was adjusted to holdthe temperature between 152 and 157° C. The rubber was dumped (removedfrom the mixer), a sheet was formed on a roll mill set at about 85° C.to 88° C., and then allowed to cool to ambient temperature.

In the second step, Masterbatch was recharged into the mixer. Themixer's speed was 80 rpm, the cooling water was set at 71° C. and thebatch pressure was set at 6 MPa. The Masterbatch was ram down mixed for30 seconds and then the temperature of the Masterbatch was brought up to149° C., and then the mixer's speed was reduce to 32 rpm and the rubberwas mixed for 3 minutes and 20 seconds at temperatures between 152 and157° C. After mixing, the rubber was dumped (removed from the mixer), asheet was formed on a roll mill set at about 85° C. to 88° C., and thenallowed to cool to ambient temperature.

The rubber Masterbatch and the curatives were mixed on a 15 cm×33 cm tworoll mill that was heated to between 48° C. and 52° C. The sulfur andaccelerators were added to the rubber (Masterbatch) and thoroughly mixedon the roll mill and allowed to form a sheet. The sheet was cooled toambient conditions for 24 hours before it was cured. The curingcondition was 160° C. for 20 minutes. The silated cyclic-corepolysulfides from Examples 1 and 2 were compounded into the tire treadformulation according to the above procedure and their performance wascompared to the performance of silanes which are practiced in the priorart, bis-(3-triethoxysilyl-1-propyl)disulfide (TESPD),bis-(3-triethoxysilyl-1-propyl)tetrasulfide (TESPT) and 1,2,4-tris-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane (TESHC), ComparativeExamples A-C. The test procedures were described in the following ASTMmethods:

Mooney Scorch ASTM D1646 Mooney Viscosity ASTM D1646 Oscillating DiscRheometer (ODR) ASTM D2084 Storage Modulus, Loss Modulus, ASTM D412 andD224 Tensile and Elongation DIN Abrasion DIN Procedure 53516 HeatBuildup ASTM D623 Percent Permanent Set ASTM D623 Shore A Hardness ASTMD2240

The results of this procedure are tabulated below in Table 1.

-   -   TESPD=bis-(3-triethoxy silylpropyl)disulfide    -   TESPT=bis-(3-triethoxy silylpropyl)tetrasulfide        -   TESHC=1,2,4-tris-(6-triethoxysilyl-3,4-dithiaheptyl)cyclohexane

TABLE 1 Example Number Ingredients Units Comp. Ex. A Comp. Ex B Comp.Ex. C Example 3 Example 4 Example 5 Masterbatch SMR-10, natural rubberphr 10.00 10.00 10.00 10.00 10.00 10.00 Budene 1207, polybutadiene phr35.00 35.00 35.00 35.00 35.00 35.00 Buna VSL 5025-1, oil-ext. sSBR phr75.63 75.63 75.63 75.63 75.63 75.63 N339, carbon black phr 12.00 12.0012.00 12.00 12.00 12.00 Ultrasil VN3 GR, silica phr 85.00 85.00 85.0085.00 85.00 85.00 Sundex 8125TN, process oil phr 6.37 6.37 6.37 6.376.37 6.37 Erucical H102 rapeseed oil phr 5.00 5.00 5.00 5.00 5.00 5.00Flexzone 7P, antiozonant phr 2.00 2.00 2.00 2.00 2.00 2.00 TMQ phr 2.002.00 2.00 2.00 2.00 2.00 Sunproof Improved, wax phr 2.50 2.50 2.50 2.502.50 2.50 Kadox 720C, zinc oxide phr 2.50 2.50 2.50 2.50 2.50 2.50Industrene R, stearic acid phr 1.00 1.00 1.00 1.00 1.00 1.00 AktiplastST, disperser phr 4.00 4.00 4.00 4.00 4.00 4.00 Silane TESPD phr 6.00Silane TESPT phr 6.80 Silane TESHC phr 8.20 Silane, Example 1 phr 7.90Silane, Example 2 phr 6 9 Catalysts Naugex MBT phr 0.10 CBS phr 2.002.00 2.00 2.00 2.00 2.00 Diphenyl guanidine phr 2.00 2.00 2.00 2.00 2.002.00 Rubbermakers sulfur 167 phr 2.20 2.20 2.20 2.20 2.20 2.20 RubberProperties Mooncy Properties Viscosity at 100° C., ML1 + 4 Mooney units70 75 67 68 68.2 68.7 MV at 135° C., MS1+ mooney units 32.4 37 30 34.633.2 34.5 Scorch at 135° C., MS1 + t₃ min. 14.2 8.1 13.2 7.3 8.1 5 Cureat 135° C., MS1 + t₁₈ min. 18.5 13.3 17.1 11.3 13.3 9.5 Rheometer (ODR)Properties, 1° arc at 149° C. M_(L) dN-m 8.9 10.1 8.4 8.6 8.6 9.1 M_(H)dN-m 34.9 38.9 38.5 35.9 32.9 37.9 t90 min. 18 17.1 14.5 11.5 17.4 13.5Physical Properties, cured to t90 at 149° C. Durometer Share “A” shore A66 69 68 66 66 69 100% Modulus MPa 2.35 2.8 2.56 2.72 2.38 2.89 300%Modulus MPa 8.54 10.86 9.06 11.42 9.79 12.32 Reinforcement Index 3.633.88 3.54 4.2 4.11 4.26 Tensile MPa 18.95 18.19 16.97 21.57 22.36 22.13Elongation % 582 448 492 505 590 500 Abrasion (DIN) mm³ 144 145 158 132138 135 Dynamic Properties in cured slate, 60° C., simple shear -non-linearity (0-10%) G′_(inital) MPa 8.1 7.7 9 4.7 6.91 6.2 ΔG′ MPa 5.85.2 6.5 2.65 4.65 3.87 G″_(max) MPa 1 0.91 1.07 0.53 0.786 0.66tanδ_(max) 0.243 0.228 0.243 0.186 0.206 0.189

Table 1, listing Comparative Examples A-C and Examples 3-5, presents theperformance parameters of silated cyclic-core polysulfide of the presentinvention, bis-(3-triethoxysilylpropyl)disulfide,bis-(3-triethoxysilylpropyl)tetrasulfide and1,2,4-tris(6-triethoxysilyl-3,4-dithiaheptyl)cyclohexane. The physicalproperties of the rubber compounded with silated cyclic-corepolysulfides from Examples 1 and 2 are consistently and substantiallyhigher than the control silanes.

The silated cyclic core polysulfide of the present invention imparthigher performance to silica-filled elastomer compositions, includingbetter coupling of the silica to the rubber, as illustrated by thehigher reinforcement index. The better reinforcing indices translateinto performance improvements for the elastomer compositions andarticles manufactured from these elastomers.

Example 6

Zeosil 1165 MP silica from Rhone-Poulenc of Lyon, France (50 grams) withthe following properties:

Characteristic Value BET surface area 180 m²/g CTAB surface area 160m²/g DOP adsorption 270 ml/100 grams Water loss at 105° C.   6% Loss onignition at 1000° C. 10.5% SiO₂ 98.5% Al₂O₃  0.4% pH 6.5is poured into a 1 liter wide-mouthed jar. The open jar is placed in aventilated oven at 105° C. and left for drying for 4 hours. The infraredabsorption differential is 1.12. To the hot silica, the silated cycliccore polysulfide from Example 2 (50 grains) is added in one portion andthe jar is closed and shaken manually for 30 seconds. The resultingcompound is a dry, free-flowing solid that does not stick to thecontainer walls.

The extraction test is performed in a 100 ml Soxhlet extractionapparatus equipped with a 250 round bottom flask. The silated corepolysulfide and silica mixture (30 grams) is placed in a paper cartridgeand acetone of dry analytical grade is placed in the flask. Theextraction test is performed in 2 hours from reflux start. The flask isheated with a heating mantle to 88° C. The cartridge is dried in anexplosion-proof oven at 110° to constant weight. The weight-loss iscalculated as a percent of extractable silane.

The mixture of the silated cyclic core polysulfide from Example 2 andsilica is an example of silica used as a carrier.

Example 7

Zeosil 1165 MP silica from Rhone-Poulenc of Lyon, France (50 grams) withthe following properties:

Characteristic Value BET surface area 180 m²/g CTAB surface area 160m²/g DOP adsorption 270 ml/100 grams Water loss at 105° C.   6% Loss onignition at 1000° C. 10.5% SiO₂ 98.5% Al₂O₃  0.4% pH 6.5

is poured into a 1 liter wide-mouthed jar. To the silica, the silatedcyclic core polysulfide from Example 2 (3.5 grams) is added in oneportion and the jar is closed and shaken manually for 10 minutes. Thejar is opened and the silated cyclic core polysulfide and silica areheated to 140° C. for 1 hour using a heating mantle and stirredvigorously using a mechanical mixer and metal stirring shaft. Heatingthe silica is intended to drive the reaction of the silated cyclic corepolysulfide with the silica and to remove the ethanol that is formed.The resulting compound is a dry, free-flowing solid that does not stickto the container walls. It is an example of a mixture where the silatedcyclic core polysulfide and silica have reacted to form an article wherethe two components are covalently bound to each other.

Example 8

SIPERNAT 22 silica from DeGussa AG of Frankfurt, Germany (50 grams) withthe following properties:

Characteristic Value BET surface area 180 m²/g CTAB surface area 160m²/g DOP adsorption 300 ml/100 grams Water loss at 105° C.  6% Loss onignition at 1000° C. 11% SiO₂ 98% Al₂O₃  0% pH 6.0is poured into a 1 liter wide-mouthed jar. To the silica the silatedcyclic-core polysulfide from Example 1 (5.3 grams) is added in oneportion and the jar is closed and shaken manually for 10 minutes. Thejar is opened and the silated cyclic core polysulfide and silica areheated to 140° C. for 1 hour using a heating mantle and stirredvigorously using a mechanical mixer and metal stirring shaft. Heatingthe silica is intended to drive the reaction of the silated cyclic corepolysulfide with the silica and to remove the ethanol that is formed.

The resulting compound is a dry, free-flowing solid that does not stickto the container walls. It is an example of a mixture where the silatedcyclic core polysulfide and silica have reacted to form an article wherethe two components are covalently bound to each other.

Example 9

N330 Carbon Black from Columbian Chemical in Marietta, Ga. (100 grams)with the following properties:

Characteristic Value BET surface area 83 m²/g CTAB surface area 82 m²/gIodine number 82 m²/gis poured into a 1 liter wide-mouthed jar. The open jar containing theN330 carbon black is placed in a ventilated oven at 120° C. and left fordrying for 2 hours. To the hot carbon black, the silated cyclic corepolysulfide from Example 2 (50 grams) is added in one portion and thejar is closed and shaken manually for 10 minutes. The resulting compoundis a dry and free-flowing black powder.

The extraction test is performed in a 100 ml Soxhlet extractionapparatus equipped with a 250 round bottom flask. The silated cycliccore polysulfide and carbon mixture (30 grams) is placed in a papercartridge and acetone of dry analytical grade is placed in the flask.The extraction test is performed in 2 hours from reflux start. The flaskis heated with a heating mantle to 88° C. The cartridge is dried in anexplosion-proof oven at 110° C. to constant weight. The weight-loss iscalculated as a percent of extractable silane.

The mixture of the silated cyclic core polysulfide from Example 2 andcarbon black is an example of filler used as a carrier. The N330 is areinforcing filler for elastomeric compositions. After the deadsorptionof the liquid silane from the carbon black in the elastomericcomposition, the carbon black functions as a reinforcing filler.

Example 10 The Use of Silated Cyclic-Core Polysulfides and SilicaMixtures in Low Rolling Resistant Tire Tread Formulation

A model low rolling resistance passenger tire tread formulation that isdescribed in Table 1, except that 12 phr silated cyclic-core polysulfideand silica mixture of Example 6 replaces the silane from Example 2 andthe Ultrasil VN3 GR silica loading was adjusted to 79 phr, is used toevaluate the performance of the silated core polysulfide on a silicacarrier. The rubber compound is prepared according to the mix procedurethat is described in Example 3. The example illustrates the utility of asilated cyclic-core polysulfide on a silica carrier.

Example 11 The Use of Silated Cyclic-Core Polysulfides and SilicaMixtures in Low Rolling Resistant Tire Tread Formulation

A model low rolling resistance passenger tire tread formulation that isdescribed in Table 1, except that 92 phr silated cyclic-core polysulfideand silica mixture of Example 7 replaces the silane from Example 2 andthe Ultrasil VN3 GR silica, is used to evaluate the performance of thesilated core polysulfide on a silica carrier. The rubber compound isprepared according to the mix procedure that is described in Example 3.The example illustrates the utility of a silated cyclic-core polysulfidethat is preformed and has coupled to the silica filler.

Example 12 The Use of Silated Cyclic-Core Polysulfides and SilicaMixtures in Low Rolling Resistant Tire Tread Formulation

A model low rolling resistance passenger tire tread formulation that isdescribed in Table 1, except that 94 phr silated cyclic-core polysulfideand silica mixture of Example 8 replaces the silane from Example 2 andthe Ultrasil VN3 GR silica, is used to evaluate the performance of thesilated cyclic-core polysulfide on a silica filler. The rubber compoundis prepared according to the mix procedure that is described in Example3. The example illustrates the utility of a silated cyclic-corepolysulfide that is preformed and has coupled to the silica fillerbefore addition to the rubber mix.

Example 13 The Use of Silated Cyclic-Core Polysulfides and Carbon BlackMixture in Low Rolling Resistant Tire Tread Formulation

A model low rolling resistance passenger tire tread formulation that isdescribed in Table 1, except that 18 phr silated cyclic core polysulfideand carbon black mixture of Example 9 replaces the silane from Example 2and the 12 phr carbon black, is used to evaluate the performance of thesilated core polysulfide on a carbon black carrier. The rubber compoundis prepared according to the mix procedure that is described in Example3. The example illustrates the utility of a silated cyclic-corepolysulfide on a carbon black carrier.

It is noted that the foregoing examples have been provided merely forthe purpose of explanation and are in no way to be construed as limitingof the present invention While the present invention has been describedwith reference to exemplary embodiments, it is understood that the wordswhich have been used herein are words of description and illustration,rather than words of limitation. Changes may be made, within the purviewof the appended claims, as presently stated and as amended, withoutdeparting from the scope and spirit of the present invention in itsaspects. Although the present invention has been described herein withreference to particular means, materials and embodiments, the presentinvention is not intended to be limited to the particulars disclosedherein; rather, the present invention extends to all functionallyequivalent structures, methods and uses, such as are within the scope ofthe appended claims.

1. A tire composition for forming a tire component, the compositionformed by combining at least a preformed free-flowing filler compositionand at least one vulcanizable rubber selected from natural rubbers,synthetic polyisoprene rubbers, polyisobutylene rubbers, polybutadienerubbers, and random styrene-butadiene rubbers (SBR); the preformedfree-flowing filler composition formed by combining at least an activefiller and a first silane; the active filler including at least one ofactive filler selected from carbon blacks, silicas, silicon basedfillers, and metal oxides present in a combined amount of at least35parts by weight per 100 parts by weight of total vulcanizable rubber,of which at least 10 parts by weight is carbon black, silica, or acombination thereof; and the first silane comprising at least onesilated cyclic core polysulfide having the general formula[Y¹R¹S_(x)—]_(m)[G¹(—SR²SiX¹X²X³)_(a)]_(n)[G²]_(o)[R³Y²]_(p) wherein:each occurrence of G¹ is independently selected from a polyvalent cyclichydrocarbon or polyvalent cyclic heterocarbon species having from 1 toabout 30 carbon atoms containing a polysulfide group represented by thegeneral formula:[(CH₂)_(b)—]_(c)R⁴[—(CH₂)_(d)S_(x)—]_(e); each occurrence of G² isindependently selected from a polyvalent cyclic hydrocarbon orpolyvalent cyclic heterocarbon species of 1 to about 30 carbon atomscontaining a polysulfide group represented by the general formula:[(CH₂)_(b)—]_(c)R⁵[—(CH₂)_(d)S_(x)—]_(e); each occurrence of R¹ and R³is independently selected from a divalent hydrocarbon fragment havingfrom 1 to about 20 carbon atoms; each occurrence of Y¹ and Y² isindependently selected from silyl (—SiX¹X²X³), hydrogen, alkoxy (—OR⁶),carboxylic acid, ester (—C(═O)OR⁶) wherein R⁶ is a monovalenthydrocarbon group having from 1 to 20 carbon atoms; each occurrence ofR² is independently selected from a divalent hydrocarbon fragment havingfrom 1 to about 20 carbon atoms that include branched and straight chainalkyl, alkenyl, alkynyl, aryl or aralkyl groups; each occurrence of R⁴is independently selected from a polyvalent cyclic hydrocarbon fragmentof 1 to about 28 carbon atom that was obtained by substitution ofhydrogen atoms equal to the sum of a+c+e, and include cyclic andpolycyclic alkyl, alkenyl, alkynyl, aryl and aralkyl groups in whicha+c+e−1hydrogens have been replaced, or a polyvalent cyclic heterocarbonfragment from 1 to 27 carbon atoms that was obtained by substitution ofhydrogen atoms equal to the sum of a+c+e; each occurrence of R⁵ isindependently selected from a polyvalent cyclic hydrocarbon fragment of1 to about 28 carbon atom that was obtained by substitution of hydrogenatoms equal to the sum of c+e and include cyclic and polycyclic alkyl,alkenyl, alkynyl, aryl and aralkyl groups in which c+e−1 hydrogens havebeen replaced, or a polyvalent cyclic heterocarbon fragment from 1 to 27carbon atoms that was obtained by substitution of hydrogen atoms equalto the sum of c+e; each occurrence of X¹ is independently selected from—Cl, —Br, —OH, —OR⁶, and R⁶C(═O)O—, wherein R⁶ is a monovalenthydrocarbon group having from 1 to 20 carbon atoms; each occurrence ofX² and X³ is independently selected from hydrogen, R⁶, wherein R⁶ is amonovalent hydrocarbon group having from 1 to 20 carbon atoms, X¹,wherein X¹ is independently selected from —Cl, —Br, —OH, —OR⁶, andR⁶C(═O)O—, wherein R⁶ is a monovalent hydrocarbon group having from 1 to20 carbon atoms, and —OSi containing groups that result from thecondensation of silanols; and each occurrence of the subscripts, a, b,c, d, e, m, n, o, p, and x, is independently given by a, c and e are 1to about 3; b is 1 to about 5; d is 1 to about 5; m and p are 1 to about100; n is 1 to about 15; o is 0 to about 10; and x is 1 to about 10; andwherein the tire composition is formulated to be vulcanizable to form atire component compound having a Shore A Hardness of not less than 40and not greater than 95 and a glass-transition temperature Tg (E″_(max))not less than −80° C. and not greater than 0° C.
 2. The tire compositionof claim 1 wherein the preformed, free-flowing filler compositionfurther comprises a second silane having the general formula[X¹X²X³SiR¹S_(x)R³SiX¹X²X³] wherein each occurrence of R¹ and R³ arechosen independently from a divalent hydrocarbon fragment having from 1to about 20 carbon atoms that include branched and straight chain alkyl,alkenyl, alkynyl, aryl or aralkyl groups wherein one hydrogen atom wassubstituted with a silyl group, (—SiX¹X²X³), wherein X¹ is independentlyselected from —Cl, —Br, —OH, —OR⁶, and R⁶C(═O)O—, wherein R⁶ is anymonovalent hydrocarbon group having from 1 to 20 carbon atoms, andincludes branched or straight chain alkyl, alkenyl, aryl or aralkylgroup and X² and X³ is independently selected from hydrogen, R⁶, X¹, and—OSi containing groups that result from the condensation of silanols;and x is 1 to about
 10. 3. The tire composition of claim 2 wherein thefiller is a mixture of filler chemically inert relative to at least oneof the first silane or second silane and filler which is chemicallyreactive to at least one of the first silane or second silane andchemically bonded thereto.
 4. The tire composition of claim 3 whereinthe inert filler is carbon black and the chemically reactive filler is asilica.
 5. The tire composition of claim 2 containing from about 0.1 to19 weight percent first silane or mixture of first silane and secondsilane.
 6. The tire composition of claim 2 containing from about 0.1 to20 weight percent first silane or mixture of first silane and secondsilane.
 7. The tire composition of claim 2 containing about 0.1 to 70weight percent first silane or mixture of first silane and secondsilane.
 8. The tire composition of claim 2 wherein the silane is amixture of first silane and second silane in a weight ratio of fromabout 0.43 to about
 99. 9. The tire composition of claim 2 wherein thesilane is a mixture of first silane and second silane in a weight ratioof from about 1 to about
 19. 10. The tire composition of claim 1 whereinthe filler is chemically inert relative to silane.
 11. The tirecomposition of claim 10 wherein the filler is carbon black.
 12. The tirecomposition of claim 1 wherein the filler is chemically reactive to thesilane and silane is chemically bonded to said chemically reactivefiller.
 13. The tire composition of claim 12 wherein the chemicallyreactive filler possesses surface inorganic hydroxyl functionality. 14.The tire composition of claim 13 wherein the chemically reactive filleris a siliceous material.
 15. The tire composition of claim 14 whereinthe siliceous material is a silica.
 16. The tire composition of claim 1wherein the silated cyclic core polysulfide is any of the isomers of4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;2-(6-thethoxysilyl-3-thiahexyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(1-methyl-5-triethoxysilyl-2-thiapentyl)-1,2-bis-(1-methyl-8-triethoxysilyl-2,3,4,5-tetrathiaoctyl)cyclohexane;4-(5-triethoxysilyl-3-thiapentyl)-1,2-bis-(8-triethoxysilyl-3,4,5,6-tetrathiaoctyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(12-triethoxysilyl-3,4,5,6-tetrathiadodecyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(11-triethoxysilyl-3,4,5,6-tetrathiaunidecyl)cyclohexane;4-(3-triethoxysilyl-1-thiapropyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6,7-pentathiatridecyl)cyclohexane;4-(6-diethoxymethylsilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(4-triethoxysilyl-2-thiabutyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(7-triethoxysilyl-3-thiaheptyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)cyclohexane;4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)benzene;4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)benzene;4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4-dithianonyl)benzene;bis-2-[4-(3-triethoxysilyl-2-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyltetrasulfide;bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyltrisulfide;bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyldisulfide;bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)phenyl]ethyltetrasulfide;bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)nathyl]ethyltetrasulfide;bis-2-[4-(4-diethoxymethylsilyl-2-thiabutyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)phenyl]ethyltrisulfide;bis-2-[4-(1-methyl-5-triethoxysilyl-2-thiapentyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cycloheptyl]ethyldisulfide;bis-2-[4-(4-triethoxysilyl-2-thiabutyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclooctyl]ethyldisulfide;bis-2-[4-(4-triethoxysilyl-2-thiabutyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclododecyl]ethyldisulfide,4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane;4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane;and mixtures thereof.
 17. The tire composition of claim 16 wherein thefiller is chemically inert relative to silane.
 18. The tire compositionof claim 17 wherein the filler is carbon black.
 19. The tire compositionof claim 16 wherein the filler is chemically reactive to the silane andsilane is chemically bonded to said chemically reactive filler.
 20. Thetire composition of claim 19 wherein the chemically reactive fillerpossesses surface metal hydroxyl functionality.
 21. The tire compositionof claim 20 wherein the chemically reactive filler is a siliceousmaterial.
 22. The tire composition of claim 21 wherein the siliceousmaterial is a silica.
 23. The tire composition of claim 19 wherein thefiller is a mixture of filler chemically inert relative to the silaneand filler which is chemically reactive to the silane and chemicallybonded thereto.
 24. The tire composition of claim 23 wherein the inertfiller is carbon black and the chemically reactive filler is a silica.25. The tire composition of claim 1 wherein the at least onevulcanizable rubber comprises emulsion polymerization derivedstyrene/butadiene having a styrene content of about 20 to about 28weight percent.
 26. The tire composition of claim 1 wherein the emulsionpolymerization derived styrene/butadiene has a styrene content of about30 to about 45 weight percent.
 27. The tire composition of claim 1wherein the at least one vulvanizable rubber comprises emulsionpolymerization prepared styrene/butadiene/acrylonitrile terpolymerrubber containing from about 2 to about 40 weight percent acrylonitrile.28. The tire composition according to claim 1 wherein the silated cycliccore polysulfide comprises any isomer of(6-triethoxysilyl-3-thia-1-hexyl)-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane.29. The tire composition according to claim 1 wherein the silated cycliccore polysulfide comprises any isomer of(6-triethoxysilyl-3-thia-1-hexyl)-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane.30. The tire composition of claim 1, further comprising curative and,optionally, at least one other additive selected from sulfur compounds,activators, retarders, accelerators, processing additives, oils,plasticizers, tackifying resins, silicas, fillers, pigments, fattyacids, zinc oxide, waxes, antioxidants and antiozonants, peptizingagents, reinforcing materials, and mixtures thereof.
 31. A tire at leastone component of which comprises a cured rubber composition obtainedfrom the tire composition of claim
 1. 32. A tire tread which comprises acured rubber composition obtained from the rubber composition ofclaim
 1. 33. A tire component comprising a cured rubber compositionobtained from the tire composition of claim
 1. 34. An uncured tirecomponent comprising a rubber composition obtained from the tirecomposition of claim 1.